US4652356A - Ion exchange membrane and electrolytic cell using thereof - Google Patents

Ion exchange membrane and electrolytic cell using thereof Download PDF

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US4652356A
US4652356A US06/355,312 US35531282A US4652356A US 4652356 A US4652356 A US 4652356A US 35531282 A US35531282 A US 35531282A US 4652356 A US4652356 A US 4652356A
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Prior art keywords
exchange membrane
membrane
ion exchange
particles
groups
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Yoshio Oda
Takeshi Morimoto
Kohji Suzuki
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AGC Inc
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Asahi Glass Co Ltd
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Assigned to ASAHI GLASS COMPANY LTD. reassignment ASAHI GLASS COMPANY LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MORIMOTO, TAKESHI, ODA, YOSHIO, SUZUKI, KOHJI
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • C08J5/2281—Heterogeneous membranes fluorine containing heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a cation exchange membrane and an electrolytic cell using thereof. More particularly, it relates to a cation exchange membrane and an electrolytic cell using thereof suitable for an electrolysis of water or an aqueous solution of an acid, a base, an alkali metal halide or an alkali metal carbonate.
  • a diaphragm method As a process for producing an alkali metal hydroxide and chlorine by an electrolysis of an aqueous solution of an alkali metal chloride, a diaphragm method has been mainly employed instead of a mercury method in view of a prevention of a public pollution. Moreover, an ion exchange membrane method has been practically operated to produce an alkali metal hydroxide having high concentration in high purity
  • the inventors have studied to operate an electrolysis of an aqueous solution at a minimized load voltage and have found that the purpose has been satisfactorily attained by using a cation exchange membrane having a gas and liquid permeable porous non-electrode layer on at least one of surfaces of the cation exchange membrane facing to an anode or a cathode which is proposed in European Patent Publication No. 0029751 or U.S. Ser. No. 205,567.
  • the effect for reducing a cell voltage by the use of the cation exchange membrane having such porous layer on the surface is depending upon a kind of the material, a porosity and a thickness of the porous layer.
  • a cation exchange membrane for electrolysis which comprises a gas and liquid permeable porous non-electrode layer on at least one surface of said membrane wherein said porous layer is formed by many conductive or non-conductive particles or particle groups which are partially or wholly discontinuously bonded on said membrane.
  • FIG. 1 is a partially sectional view of one embodiment of a cation exchange membrane of the present invention
  • FIG. 2 is a plane view of one embodiment of the cation exchange membrane
  • FIGS. 3(i)-3(ii) are sectional views for illustrating a calculation of a thickness of a porous layer made of particles or particle groups.
  • FIGS. 4 to 7 are plane view of each membrane having each pattern of particles or particle groups of the present invention.
  • the effect for reducing a content of particles for the gas and liquid permeable porous non-electrode layer is remarkably advantageous. It is economically advantageous in the case of expensive particles and it is easy to form the porous layer on the membrane. Moreover, the characteristics of the resulting membrane are not inferior to those of a membrane having a thick porous layer formed with a lot of particles. Sometimes, the resulting membrane results in superior current efficiency to be noticeably advantageous in a practical operation.
  • FIG. 1 is a partially sectional view of one embodiment of a cation exchange membrane of the present invention wherein the membrane (1) has each porous layer on both surfaces of the membrane.
  • the porous layer is formed by many particles (2) or particle groups (3) which are particle masses formed by aggregation of the particles.
  • the particles (2) or the particle groups (3) are separately or discontinuously bonded on the membrane respectively.
  • FIG. 2 This condition is understood in FIG. 2 as the plane view of one embodiment of an ion exchange membrane.
  • an amount of the particles or the particle groups which are bonded on the surface of the membrane to form the porous layer is depending upon a kind and a size of the particles. According to the studies, it is found that the numer of the particles is preferably in a range of 5-10 12 /cm 2 especially 10-2 ⁇ 10 11 /cm 2 .
  • the particles or the particle groups can be partially or wholly discontinuously bonded in a form of a continuous pattern.
  • the ratio of the parts of the surface of the membrance on which any particle or particle group is bonded to the whole surface of the membrane is in the range of 5-90%, especially 10-80%. Further the dimension of such parts is preferably in the range of 100 ⁇ -5 mm, especially 100 ⁇ -3 mm.
  • the continuous pattern as a whole view is formed.
  • the discontinuous porous layer (12) can be formed in the continuous pattern on the membrane (11).
  • the porous layers 12, 12' can be formed in the discontinuous pattern, but it is a continuous pattern as a whole.
  • the porous layers can be in a form of combination of a discontinuous pattern 12 and a continuous pattern 12' on the membrane (11).
  • An amount of the particles or the particle groups bonded is perferably in a range of 0.001-5 mg/cm 2 , especially 0.005-2.0 mg/cm 2 based on the unit area of the surface of the membrane.
  • the particles for the gas and liquid permeable porous layer formed on the cation exchange membrane can be conductive or non-conductive and can be made of an inorganic or organic material as far as the particles do not impart an electrode function. It is preferable to be made of a material having high corrosion resistance to an electrolyte an evolved gas at electrode, such as metals, oxides, hydroxides, carbides, nitrides of metals and mixtures thereof, and corrosion resistance polymers especially fluorinated polymers.
  • the porous layer in the anode side can be made of a powder selected from the group consisting of metals in IV-A Group (preferably Ge, Sn, Pb); metals in IV-B Group (preferably Ti, Zr, Hf); metals in V-B Group (preferably Nb, Ta); metals in iron Group (Fe, Co, Ni) or alloys, oxides, hydroxides, nitrides and carbides thereof.
  • the porous layer in the cathode side can be a powder used for the porous layer in the anode side and also silver, stainless steel and carbon (active carbon, graphite etc.).
  • the material is preferably used in a form of a powder having a particle diameter of 0.01-300 ⁇ especially 0.1-100 ⁇ .
  • a binder of a fluorocarbon polymer such as polytetrafluoroethylene, and polyhexafluoropropylene
  • a thickener of a cellulose derivative such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose
  • a water soluble thickener such as polyethyleneglycol, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, polymethyl vinyl ether, casein and polyacrylamide.
  • the binder or the thickener is preferably used at a ratio of 1-50 wt.% especially 0.5-30 wt.% based on the powder.
  • the bonding of the particles or the particle groups for the porous layer on the ion exchange membrane is carried out by thoroughly mixing the conductive or non-conductive particles, if necessary, a binder or a thickener in a desired medium such as an alcohol or a hydrocarbon to prepare a paste of the mixture and coating the paste on the membrane by a screen printing etc.
  • the particles or the particle groups can be adhered on the membrane by preparing a syrup or slurry of the mixture instead of the paste of the mixture of the particles and spraying it on the membrane.
  • the process and method of formation of the porous layer on the membrane in a thin pattern are not critical and can be various processes such as a screen printing process, a spraying process and also a transcription-printing process and a roll coating process.
  • the screen printing process the paste is printed through a screen having a desired pattern which is previously prepared.
  • the roll printing process it is printed by a roll having a desired pattern which is previously engraved.
  • the particles or particle groups for the porous layer adhered on the ion exchange membrane are preferably heat press-bonded at 80°-220° C. by a press or a roll under a pressure of 1-150 kg/cm 2 or under a pressure of 1-100 kg/cm 2 respectively.
  • the particles or particle groups are preferably partially embedded into the membrane.
  • the porous layer made of the particles or particle groups bonded on the membrane preferably has a porosity of 30-99%, especially 40-95% and a thickness of 0.01-100 ⁇ preferably 0.1-50 ⁇ , especially 0.5-20 ⁇ , which is less than that of the membrane.
  • the thickness of the porous layer made of the particles or particle groups is given by the size (a) in the case of the uniform size of the particles or particle groups as shown in FIG. 3(i) and is given by an average size (b) in the case of non-uniform sizes of the particles or particle groups as shown in FIG. 3(ii).
  • the porosity of the porous layer is given by a calculation of the aforementioned thickness of the porous layer.
  • the ion exchange membrane having the porous layer on the membrane is preferably a membrane having cation exchange groups such as carboxylic acid groups, sulfonic acid groups, phosphoric acid groups or phenolic hydroxy groups preferably a membrane made of a fluorinated polymer especially a copolymer of a vinyl monomer such as tetrafluoroethylene or chlorotrifluoroethylene and a fluorovinyl monomer having an ion exchange group such as sulfonic acid group, carboxylic acid group or phosphoric acid group.
  • a cation exchange membrane having an ion exchange group content of 0.5 to 4.0 meq/g.dry polymer especially 0.8 to 2.0 meq/g.dry polymer.
  • the ratio of the units (N) is preferably in a range of 1 to 40 mol % especially 3 to 25 mol.%.
  • the cation exchange membrane used in the present invention is not limited to be made of only one kind of the polymer or the polymer having only one kind of the ion exchange group. It is possible to use a laminated membrane made of two kinds of polymers having smaller ion exchange group content in the cathode side or an ion exchange membrane having weak acidic exchange groups such as carboxylic acid groups in the cathode side and strong acidic exchange groups such as sulfonic acid groups in the anode side.
  • the ion exchange membrane can be prepared by the conventional process and can be reinforced with a fabric such as a woven fabric and a net; a nonwoven fabric a metallic mesh or a porous substrate.
  • a thickness of the ion exchange membrane is preferably in a range of 50 to 1000 ⁇ preferably 100 to 500 ⁇ .
  • the bonding can be carried out in a desired form of the ion exchange groups for preventing the decomposition of the ion exchange groups for example, an acid form or an ester form in the case of carboxylic acid groups and a --SO 2 F form in the case of sulfonic acid groups.
  • Various kinds of the electrodes can be used together with the membrane of the present invention.
  • foraminous electrodes such as a porous plate, a net, a punched metal or an expanded metal can be used.
  • an expanded metal having a major length of 1.0-10 mm; a minor length of 0.5-10 mm; a mesh width of 0.1-1.3 mm and a ratio of opening area of 30-90% is used.
  • Plural plate-like electrodes can be also used. It is preferable to use plural electrodes having different ratio of opening area to place the electrode having a smaller ratio of opening area in the side of the membrane.
  • the anode is usually made of a platinum group metal, a conductive platinum group metal oxide or reduced-oxide.
  • the cathode is usually made of a platinum group metal, a conductive platinum group oxide or iron group metal.
  • the platinum group metal can be Pt, Rh, Ru, Pd and Ir.
  • the iron group metal can be Fe, Co, Ni, Raney nickel, a stabilized Raney nickel, stainless steel, an alkali etching stainless stell (U.S. Pat. No. 4,255,247), Raney nickel plated cathode (U.S. Pat. Nos. 4,170,536 and 4,116,804), a nickel rhodanate plated cathode (U.S. Pat. Nos. 4,190,514 and 4,190,516).
  • the electrode can be prepared by using the material for the anode or the cathode itself.
  • the platinum group metal or the conductive platinum group metal oxide is used the material is preferably coated on the surface of an expanded metal made of a valve metal such as titanium and tantalum.
  • the electrode When the electrode is assembled in the present invention, the electrode is preferably placed in contact with an ion exchange membrane. It can be placed to depart from the ion exchange membrane with a desired gap, although the reduction of the cell voltage is not remarkable.
  • the electrode When the electrode is placed in contact with the porous layer on the ion exchange membrane, it is preferable to contact it under a low pressure such as 0-2.0 kg/cm rather than high pressure.
  • the electrode placed in the side of the ion exchange membrane on which a porous layer is not formed can be placed with or without contacting with the surface of the ion exchange membrane.
  • the electrolytic cell used in the present invention can be a monopolar or bipolar type in the aforementioned structure.
  • the material for the cell used in the electrolysis of an aqueous solution of an alkali metal chloride is made of a material being resistant to an aqueous solution of an alkali metal chloride and chlorine in the anode compartment such as valve metals and titanium and being resistant to an alkali metal hydroxide and hydrogen in the cathode compartment such as iron, stainless steel and nickel.
  • the condition of the process for electrolysis of an alkali metal chloride can be the known condition disclosed in the prior art Japanese Unexamined Patent Publication No. 112398/1979.
  • An aqueous solution of an alkali metal chloride having a concentration of 2.5-5.0 normal (N) is preferably fed into the anode compartment and water or a dilute solution of an alkali metal hydroxide is fed into the cathode compartment and an electrolysis is preferably performed at 80° C.-120° C. and at a current density of 10-100 A/dm 2 .
  • an electrolysis it is preferable to minimize heavy metal ions such as calcium ions and magnesium ions because such ions cause deterioration of the ion exchange membrane.
  • an acid such as hydrochloric acid in the aqueous solution of an alkali metal chloride.
  • the use of the membrane has been mainly illustrated in the case of the electrolysis of an aqueous solution of an alkali metal chloride.
  • the membrane can be, of course, used in an electrolysis of water, a hydrogen halide acid (HCl, HBr), or an alkali metal carbonate.
  • the paste was printed by a screen printing on a surface of a cation exchange membrane made of a copolymer of CF 2 ⁇ CF 2 and CF 2 ⁇ CFO(CF 2 ) 3 COOCH 3 (ion exchange capacity of 1.44 meq/g.dry polymer; thickness of 280 ⁇ ) as a printing substrate in the anode side with a screen made of polyethyleneterephthalate (mesh of 200; thickness of 75 ⁇ ) a printing plate having a screen mask (thickness of 30 ⁇ ) and a polyurethane squeezer.
  • the coated layer on the membrane was dried.
  • the same rutile type titanium oxide powder was coated, in the side of the cathode, on the surface of the membrane having the porous layer in the anode side by the same manner. Both particle layers were press-bonded on the surfaces of the ion exchange membrane at 140° C. under a pressure of 30 kg/cm 2 .
  • the ion exchange membrane was hydrolyzed by dipping into 25 wt.% aqueous solution of an alkali metal hydroxide at 90° C. for 16 hours.
  • the titanium oxide particles were bonded at a content of 0.7 mg/cm 2 .
  • the titanium oxide particles or particle groups are separately bonded on the membrane in a height of the particles of about 20 ⁇ from the level of the membrane.
  • Example 1 In accordance with the process of Example 1 except varying the composition of the paste by using each kind of particles having each particle diameter at each content shown in Table 1 and using no modified PTFE in Examples 2, 4, 6 and 9, each cation exchange membrane having porous layers on both surfaces was prepared.
  • the particles were prepared, if necessary, by crushing commercial products and sieving to classify particles in the ranges shown in Table 1.
  • the particles or particle groups were separately bonded on the membrane.
  • a suspension of 10 g. of titanium oxide powder having a particle diameter of 2-5 ⁇ and 1 g. of a modified PTFE powder of polytetrafluoroethylene having a particle diameter of 1 ⁇ or less coated with a copolymer of CF 2 ⁇ CF 2 and CF 2 ⁇ CFO(CF 2 ) 3 COOCH 3 in 100 ml. of water was sprayed by a spray gun on both surfaces of an ion exchange membrane made of a copolymer of CF 2 ⁇ CF 2 and CF 2 ⁇ CFO(CF 2 ) 3 COOCH 3 having an ion exchange capacity of 1.43 meq/g.dry polymer and a thickness of 280 ⁇ which was placed on a hot plate at 140° C.
  • the spraying rate was controlled so as to dry up water in the sprayed suspension for 15 sec. or shorter.
  • the porous layers formed by the spraying were press-bonded on the ion exchange membrane at 140° C. under a pressure of 30 kg/cm 2 .
  • the ion exchange membrane was hydrolyzed by dipping into 25 wt.% aqueous solution of an alkali metal hydroxide at 90° C.
  • the titanium oxide particles were bonded at a content of 0.2 mg/cm 2 .
  • Example 2 In accordance with the process of Example 1 except using a cation exchange membrane made of a copolymer of CF 2 ⁇ CF 2 and CF 2 ⁇ CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F (ion exchange capacity of 0.87 meq/g. dry polymer: thickness of 300 ⁇ ), an ion exchange membrane having each layer of titanium oxide particles having a particle diameter of 10-20 ⁇ at a content of 1.0 mg/cm 2 on both surfaces in the anode side and the cathode side was obtained.
  • a cation exchange membrane made of a copolymer of CF 2 ⁇ CF 2 and CF 2 ⁇ CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F (ion exchange capacity of 0.87 meq/g. dry polymer: thickness of 300 ⁇
  • An anode having low chlorine overvoltage which was made of a titanium expanded metal (minor length of 2.5 mm; major length of 5 mm) coated with a solid solution of ruthenium oxide, iridium oxide and titanium oxide was placed in the anode side and a cathode having low hydrogen overvoltage which was made of a SUS 304 expanded metal (minor length of 2.5 mm; major length of 5 mm) etched in 52 wt.% of aqueous solution of NaOH at 150° C. for 152 hours was placed in the cathode side of contact them with each ion exchange membrane under a pressure to form a cell.
  • Test electrodes used in Test No. 1 were used to contact them with each ion exchange membrane having porous layers under a pressure to form each cell.
  • An anode made of a nickel expanded metal (minor length of 2.5 mm; major length of 5 mm) was placed in the anode side and a cathode having low hydrogen overvoltage which is made of a SUS 304 expanded metal (minor length of 2.5 mm; major length of 5 mm) etched in 52% NaOH at 150° C. for 52 hours was placed in the cathode side to contact them with each ion exchange membrane under a pressure.
  • the paste was printed by a screen printing on a surface of a cation exchange membrane made of a copolymer of CF 2 ⁇ CF 2 and CF 2 ⁇ CFO(CF 2 ) 3 COOCH 3 (ion exchange capacity of 1.44 meq/g.dry polymer; thickness of 280 ⁇ ) as a printed substrate in anode side with a screen made of polyethyleneterephthalate (mesh of 200; thickness of 75 ⁇ ) a printing plate having a screen mask (thickness of 30 ⁇ ) and a polyurethane squeezer to give a pattern shown in FIG. 4.
  • each square having a side of 1 mm was arranged with a gap to the adjacent square and a ratio of the coated area was 70%.
  • the coated membrane was dried.
  • tin dioxide particles having the same particle diameter were also coated by the same manner on the surface in the cathode side and both particle layers were press-bonded to the ion exchange membrane at 140° C. under a pressure of 30 kg/cm 2 .
  • the ion exchange membrane was hydrolyzed by dipping it into 25 wt.% NaOH at 90° C. for 16 hours.
  • an amount of titanium oxide particles was 0.5 mg/cm 2 and a content of tin dioxide particles was 0.4 mg/cm 2 .
  • Example 12 In accordance with the process of Example 12 except varying the composition of the paste by using each kind of particles having each particle diameter at each content shown in Table 6, each cation exchange membrane having porous layers on both surfaces was prepared.
  • the particles were prepared, if necessary, by crushing commercial products and sieving to classify particles in the range shown in Table 6.

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US06/355,312 1981-03-20 1982-03-05 Ion exchange membrane and electrolytic cell using thereof Expired - Fee Related US4652356A (en)

Applications Claiming Priority (3)

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JP56-39620 1981-03-20
JP56039620A JPS57172927A (en) 1981-03-20 1981-03-20 Cation exchange membrane for electrolysis
JP56-74165 1982-06-12

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US06/205,567 Continuation-In-Part US4666574A (en) 1979-11-27 1980-11-10 Ion exchange membrane cell and electrolytic process using thereof

Related Child Applications (2)

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US06/381,745 Continuation-In-Part US4655886A (en) 1980-11-10 1982-05-24 Ion exchange membrane cell and electrolysis with use thereof
US06/381,746 Continuation US4661218A (en) 1979-11-27 1982-05-24 Ion exchange membrane cell and electrolysis with use thereof

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EP (1) EP0061594B1 (de)
JP (1) JPS57172927A (de)
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US4889577A (en) * 1986-12-19 1989-12-26 The Dow Chemical Company Method for making an improved supported membrane/electrode structure combination wherein catalytically active particles are coated onto the membrane
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WO2000034033A1 (en) * 1998-12-04 2000-06-15 The Regents Of The University Of California Novel controllable ion-exchange membranes
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US20050130024A1 (en) * 2003-12-10 2005-06-16 Jsr Corporation Proton conductive composition and proton conductive membrane
CN103993329A (zh) * 2014-06-06 2014-08-20 山东东岳高分子材料有限公司 离子传导膜及其制备方法
CN104018181A (zh) * 2014-06-06 2014-09-03 山东东岳高分子材料有限公司 用于氯碱工业的新型离子传导膜及其制备方法
CN104018180A (zh) * 2014-06-06 2014-09-03 山东东岳高分子材料有限公司 零极距离子交换膜及其制备方法
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JPS57174482A (en) * 1981-03-24 1982-10-27 Asahi Glass Co Ltd Cation exchange membrane for electrolysis
JPS6049718B2 (ja) * 1983-08-12 1985-11-05 旭硝子株式会社 塩化アルカリ電解槽
EP0163975B1 (de) * 1984-05-15 1988-08-10 Asahi Glass Company Ltd. Verfahren zur Herstellung von Trifluoressigsäure und Trifluoracetylchlorid
EP0253119A3 (de) * 1986-06-13 1989-07-19 Asahi Glass Company Ltd. Ionenaustauschermembran für die Elektrolyse
GB2320928B (en) * 1994-03-25 1998-10-28 Nec Corp Method for producing electrolyzed water
JP2830733B2 (ja) * 1994-03-25 1998-12-02 日本電気株式会社 電解水生成方法および電解水生成機構
ZA952384B (en) * 1994-04-13 1996-09-23 Nat Power Plc Cation exchange membranes and method for the preparation of such membranes
CN104018179B (zh) * 2014-06-06 2017-01-04 山东东岳高分子材料有限公司 离子传导膜及其制备方法

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US4752370A (en) * 1986-12-19 1988-06-21 The Dow Chemical Company Supported membrane/electrode structure combination wherein catalytically active particles are coated onto the membrane
US4889577A (en) * 1986-12-19 1989-12-26 The Dow Chemical Company Method for making an improved supported membrane/electrode structure combination wherein catalytically active particles are coated onto the membrane
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US6811911B1 (en) 1998-02-24 2004-11-02 Tel Aviv University Future Technology Development L.P. Ion conductive matrixes and their use
EP1066656A1 (de) * 1998-02-24 2001-01-10 Tel-Aviv University Future Technology Development L.P. Ionenleitende matrizen und deren verwendung
EP1066656A4 (de) * 1998-02-24 2001-05-30 Univ Ramot Ionenleitende matrizen und deren verwendung
US6074692A (en) * 1998-04-10 2000-06-13 General Motors Corporation Method of making MEA for PEM/SPE fuel cell
WO2000034033A1 (en) * 1998-12-04 2000-06-15 The Regents Of The University Of California Novel controllable ion-exchange membranes
US6468657B1 (en) 1998-12-04 2002-10-22 The Regents Of The University Of California Controllable ion-exchange membranes
US20020093008A1 (en) * 1999-04-30 2002-07-18 Jochen Kerres Proton-conducting ceramic/polymer composite membrane for the temperature range up to 300°C
WO2000077080A1 (de) * 1999-04-30 2000-12-21 Universität Stuttgart Institut Für Physikalische Elektronik Protonenleitende keramik-polymer-kompositmembran für den temperaturbereich bis 300 °c
US20040251450A1 (en) * 1999-04-30 2004-12-16 Jochen Kerres Proton-conducting ceramic/polymer composite membrane for the temperature range up to 300 degree C
EP2476722A1 (de) * 1999-04-30 2012-07-18 Häring, Thomas Protonenleitende Keramik-Polymer-Kompositmembran für den Temperaturbereich bis 300°C
EP1217099A2 (de) * 2000-12-21 2002-06-26 CPC Cellular Process Chemistry Systems GmbH Mikroreaktor für elektrochemische Umsetzungen
EP1217099A3 (de) * 2000-12-21 2002-07-10 CPC Cellular Process Chemistry Systems GmbH Mikroreaktor für elektrochemische Umsetzungen
US20050130024A1 (en) * 2003-12-10 2005-06-16 Jsr Corporation Proton conductive composition and proton conductive membrane
US10633499B2 (en) * 2014-01-27 2020-04-28 Fujifilm Manufacturing Europe B.V. Process for preparing membranes
CN103993329A (zh) * 2014-06-06 2014-08-20 山东东岳高分子材料有限公司 离子传导膜及其制备方法
CN104018180A (zh) * 2014-06-06 2014-09-03 山东东岳高分子材料有限公司 零极距离子交换膜及其制备方法
CN104018180B (zh) * 2014-06-06 2016-10-05 山东东岳高分子材料有限公司 零极距离子交换膜及其制备方法
CN103993329B (zh) * 2014-06-06 2017-01-04 山东东岳高分子材料有限公司 离子传导膜及其制备方法
CN104018181B (zh) * 2014-06-06 2017-01-11 山东东岳高分子材料有限公司 用于氯碱工业的离子传导膜及其制备方法
CN104018181A (zh) * 2014-06-06 2014-09-03 山东东岳高分子材料有限公司 用于氯碱工业的新型离子传导膜及其制备方法

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DE3275207D1 (en) 1987-02-26
EP0061594B1 (de) 1987-01-21
EP0061594A2 (de) 1982-10-06
JPS57172927A (en) 1982-10-25
CA1189829A (en) 1985-07-02
JPH0116630B2 (de) 1989-03-27
EP0061594A3 (en) 1983-02-16

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